阴极电泳涂料用树脂—改性聚丁二烯合成工艺研究

液体聚丁二烯（ＬＰＢ）与过氧乙酸反应生成的环氧化聚丁二烯（ＯＰＢ）再与胺化剂反应生成胺化环氧化聚丁二烯（ＤＯＰＢ）是性能优良的电泳涂料用树脂。实验结果表明ＬＰＢ环氧化反应温度只能在１５￣６０℃进行，且高温反应时间不能超过５小时；ＬＰＢ的分子量低，则环氧值增大。ＯＰＢ的胺化反应最佳温度为１１０℃，２ｈ内可完成反应。     

环氧蓖麻油合成条件优化

在无溶剂条件下制备环氧蓖麻油,对参加环氧化反应的有机酸和催化剂进行选择,研究了反应时间和反应温度对产物环氧值的影响。通过正交实验对环氧化合成条件进行优化,结果表明,蓖麻油／乙酸／双氧水／磷酸（质量比）=1：0．15：0．8：0．01,反应温度50℃,反应时间3h,所得产品环氧值达6．95％,采用FT-IR和1HNMR方法对产品进行了表征。整个过程操作简单,反应时间短,反应条件温和。     

CO2在Ag—Ba—Ca—K／α—Al2O3上的吸附及其在乙烯环氧化反应中的抑制作用

应用ＦＴＩＲ和脉冲反应技术研究了ＣＯ２和Ｏ２在Ａｇ－Ｂａ－Ｃａ－Ｋ／α－Ａｌ２Ｏ３上的吸附及ＣＯ２对Ｃ２Ｈ４环氧化，完全氧化及环氧乙烷（ＥＯ）深度氧化反应的影响。研究结果表明，ＣＯ２和表面吸附氧在负载银催化剂表面存在竞争吸附，ＣＯ２对表面吸附氧有置换作用，该作用降低了银催化剂表面吸附氧的浓度，并且所形成的碳酸根物种改善了乙烯环氧化反应活性氧种的表面分布，对Ｃ２Ｈ４的环氧化反应有一定的抑制作用，但是     

银-钡催化剂的表面性质和对乙烯环氧化的活性

电解根作为乙烯环氧化催化剂有较好的催化性能，微量助催化剂ＢａＯ能大大提高反应活性，但过多的Ｂａ会抑制反应活性和选择性。ＸＰＳ，ＩＣＰ，ＡＥＳ结果表明：钡在表面富集，反应前钡以ＢａＯ和ＢａＣＯ３形式存在，反应时以ＢａＣＯ３存在于表面。催化稳定性实验表明ＢａＯ和ＢａＣＯ３的作用相同。用功函数测量研究了氧的吸附，结合活性数据阐明了钡添加的电子效应。     

二乙胺液相催化羰化制备二乙基甲酰胺

考察了反应压力、催化剂、助催化剂和反应温度对二乙胺（ＤＥＡ）液相羰基化合成二乙基甲酰胺（ＤＥＦ）反应的影响，确定了量佳反应条件．结果表明，ＣＯ分压（Ｐ∞）对反应有明显影响，生成ＤＥＦ的速率随Ｐ∞增大而增大；催化剂浓度对反应的速率影响较小，添加剂环氧丙烷（ＰＯ）对催化剂有较强的助催化作用，而且助催化作用随ＰＯ浓度的增加而增大，生成ＤＥＦ的选择性随ＰＯ浓度的增加而降低，温度对反应也有明显的影响，确定最佳反应条件为：ＣＯ分压小于６．０ＭＰａ，反应温度为８０℃至９０℃，催化剂浓度不大于０．０５ｍｏｌ／Ｌ，助催化剂ＰＯ浓度不大于４．０ｍｏｌ／Ｌ．此时选择性不小于９６％．     

涂层阳极电氧化合成环氧环己烷

用廉价的涂层电极作为阳极，在Ｈ２Ｏ－ＮａＢｒ－ＭｅＣＮ（ＭｅＣＮ：Ｈ２Ｏ＝１：４）介质中，电流密度控制在０．４Ａ／ｄｍ＾２左右，由环己烯电化学氧化合成环氧环己烷，产率８２．６％。     

五氟代锰卟啉模拟酶体系快速混合停流吸收谱

采用快速混合停流技术,在实际反应条件下,考察了五氟代锰卟啉配合物Ｍｎ~Ⅲ（ＴＦＰＰ）Ｃ１与两种单氧给体亚碘酰苯ＰｈＩＯ和过氧苯甲酸ｍ－ＣＰＢＡ构建的细胞色素Ｐ－４５０模拟酶体系催化活性物种的生成及催化烯烃环氧化过程．在氧给体ＰｈＩＯ作用下,Ｍｎ~Ⅲ（ＴＦＰＰ）Ｃ１生成了高价锰氧卟啉配合物和双核μ－氧锰卟啉配合物,具有高的催化环氧化活性和催化剂稳定性．而在氧给体ｍ－ＣＰＢＡ作用下,Ｍｎ~Ⅲ（ＴＦＰＰ）Ｃ１则生成了一种较稳定物种,以致催化活性较低。     

多齿双亚胺双膦配位的钌络合物的制备和氢化性能

等摩尔的Ｒｕ（ＯＡｃ）２（Ｐｈ３Ｐ）２和Ｎ，Ｎ＇－双－［邻－（二苯基膦）苯亚甲基］乙二胺（简称Ｐ２Ｎ２）在回流的二氯甲烷或甲苯中反应，分别生成两个新型四齿胺膦配位的钌络合物Ｒｕ（ＯＡｃ）２Ｐ２Ｎ２．２Ｈ２Ｏ和反应式－ＲｕＣｌ２Ｐ２Ｎ２．２Ｈ２Ｏ．对两个络合物进行了元素，ＩＲ和ＮＭＲ表征。在氢压１．０至８．０ＭＰａ和反应温度３０至１５０℃的范围内，研究了它们催化α，β－不饱和酸的氢化性能。结果表明。     

环氧化聚丁二烯/酸酐体系的热固化行为研究

使用差动热分析仪 ,以等速升温热固化和等温热固化方式研究了环氧化聚丁二烯及双酚A型环氧树脂在α 甲基 四氢苯酐、顺酐、酸酐 70 # 等固化剂作用下的热固化行为 ,确定了LEPB MBA体系固化反应的活化能在71.90～ 75 .0 3kJ·mol-1之间。实验证明 ,环氧化聚丁二烯和双酚A型环氧树脂在固化行为方面存在明显的差异     

环氧化蓖麻油的合成及表征

采用酸性氧化铝做催化剂对蓖麻油(CO)进行环氧化,探索环氧化反应时间、反应温度和催化剂等不同条件对蓖麻油环氧化的影响,从而优化出合适的反应条件,采用傅立叶变换红外光谱法(FTIR)、热重分析法(TG)对制备的环氧化蓖麻油(ECO)的结构和性质等进行了研究。利用盐酸-丙酮法对环氧化产物进行环氧值的测定,结果表明,在优化条件下,即采用酸性氧化铝做催化剂,H₂O₂的滴加温度保持在50～55 ℃,反应温度65 ℃,反应时间控制在11.5 h,同时同时加入尿素做稳定剂,可以提高H₂O₂的利用率,使环氧化蓖麻油的环氧值达到2.094×10_-3 mol/g。 对ECO的性能表征结果表明,ECO粘度随着环氧值的增大而增大,随着温度的升高而降低。 ECO在250 ℃前能够基本保持稳定,而后开始分解,有3个明显的热分解阶段：250~390 ℃、390~470 ℃、470~580 ℃,ECO的热稳定性较好。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

A general and convenient synthesis of 4-(tosylmethyl)semicarbazones and their use in amidoalkylation of hydrogen,heteroatom, and carbon nucleophiles

A general synthesis of previously unknown semicarbazone-based α-amidoalkylating reagents, 4-(tosylmethyl)semicarbazones, has been developed. The synthesis involved three-component condensation of semicarbazones of aliphatic or aromatic aldehydes with the same or other aldehydes and p-toluenesulfinic acid. The scope and limitations of this reaction were investigated. The compounds obtained were demonstrated to be an efficient α-(4-semicarbazono)alkylating agents. They were reacted with H- (sodium borohydride), O- (sodium methylate), S- (sodium phenylthiolate), N- (pyrrolidine, sodium succinimide), P- (trialkyl phosphites), and C-nucleophiles (sodium diethyl malonate) to give the corresponding products of the tosyl group substitution, 4-substituted semicarbazones, including analogues of nitrofurazone. Among the prepared compounds tested in vitro for antibacterial and antifungal activity, three nitrofuryl-containing semicarbazones exhibited high biological activities with minimum inhibitory concentration (MIC) values of 8–32 μg/mL.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Synthesis of novel chiral bidentate hydroxyalkyl-N-heterocyclic carbene ligands and their application in palladium-catalyzed Mizoroki–Heck couplings and asymmetric addition of diethylzinc to benzaldehyde

A small library of new chiral bidentate hydroxyalkyl-imidazolium salts 1 is conveniently synthesized on multi-gram scale from inexpensive and commercially available chiral pool amino acids. The corresponding carbenes, generated by deprotonation of imidazolium salts 1, in combination with palladium(II) chloride were tested in the Mizoroki–Heck coupling reaction. The most significant results in terms of yields and reactivities were achieved with low catalyst loading. The catalytic activities of these imidazolium salts were also investigated in the asymmetric addition of diethylzinc to benzaldehyde. The use of MgO nanoparticles as an additive in conjunction with these ligands played a crucial role in increasing the efficiency of these reactions.